JPH01254751A - Flame-retardant olefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having modified surface and improved chemical resistance, etc., free from generation of harmful gas by combustion and suitable for electric wire, etc., by compounding specific amounts of an olefin resin silane graftmer, a malic acid (anhydride) derivative of polyethylene, etc. CONSTITUTION:The objective composition is produced by compounding (A) one or more kinds of resins selected from a copolymer of ethylene and an alpha-olefin, an ethylene-ethyl acrylate copolymer, etc., (B) silane graftmer of an olefin resin preliminarily grafted with a silane (the sum of the components A and B is 100 pts.wt.), (C) 0.1-30 pts.wt. of a maleic acid (anhydride) derivative of polyethylene, ethylene-vinyl acetate copolymer resin or ethylene-alpha-olefin copolymer, (D) 0.1-30 pts.wt. of a silicone-modified material produced by the graft polymerization of a reactive polyorganosiloxane to a thermoplastic resin and (E) 50-300 pts.wt. of a hydrated metal compound.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is a flame-retardant material that does not generate any harmful and corrosive halogen gas even when burned due to a fire, and is particularly intended for use in electric wires and cables. This invention relates to an olefin resin composition.

[Conventional technology]

Conventionally, flame retardancy has been achieved in polyolefin compositions, which are often used as insulating materials for electric wires, cables, and other electrical appliances, by adding halogen compounds and antimony trioxide to polyolefins. However, these ill animal halogen compositions generate halogen gas when burned, which is harmful to the human body, and corrodes metals, which is not desirable. In addition, due to the large amount of smoke and poor visibility, evacuation of people and firefighting activities in the event of a fire were severely restricted.

In particular, recently there has been a strong demand for not generating such halogen-based gases from the standpoint of safety. In light of this situation, inorganic flame retardants, which are hydrated metal compounds with very little smoke generation and toxicity, have been attracting attention.

In recent years, magnesium hydroxide,
It is a resin composite filled with a large amount of aluminum hydroxide, etc., but the magnesium hydroxide reacts with moisture and carbon dioxide in the air and transforms into carbonate/gnesium, causing magnesium carbonate to form on the surface of the resin composition. Crystal white matter forms.

(2) Magnesium hydroxide and aluminum hydroxide have extremely poor chemical resistance to acids and alkalis, and easily melt and elute from the surface of the resin composition. In particular, Pl+ is significantly eluted even by mild acids, which tends to cause surface deterioration.

■The surface is easily damaged because it is filled with a large amount of inorganic filler.

■The surface turns white or buckles when bent.

These problems caused a delay in the practical application of electric wires and cables.

However, patent application No. 61-12906 has already been filed in relation to the present invention.
No. 4 and Japanese Patent Application No. 61-138316, the silane graftomer does not require any help from a catalyst to promote crosslinking, and the silane graftomer can be used by combining the hydroxyl groups (one group) on the surface of the hydrated metal compound with the silane. Graftomer silanol group ()St-
Due to the influence of a small amount of moisture on the surface of the hydrated metal compound and the hydrated metal compound similar to an organometallic compound catalyst, a condensation reaction due to hydrolysis occurs in the environment of frictional heat generated during kneading, resulting in a strong siloxane. Bond (-3i-0-MmOn; M
metal). At this time, no catalyst or the like is required at all.

For this strong connection, the above-mentioned patent application No. 61-129064
No. 61-138316 specifies that it has excellent shape retention at high temperatures, prevents dripping during combustion, and is effective in improving bending whitening and abrasion resistance as mechanical properties.

In addition, the examples also describe improvements in mechanical properties, surface properties, thermal properties including thermal deformation, and flame retardant properties including oxygen index.

Traditionally, polyethylene, polypropylene, ethylene-
Anhydrous with a skeleton of liquid hydrocarbons such as vinyl acetate copolymer resin (hereinafter referred to as EVA), ethylene-ethyl acrylate copolymer resin (hereinafter referred to as EEA), copolymer of ethylene and α-olefin, and liquid polybutadiene. There are modified unsaturated dicarboxylic acids obtained by reacting maleic acid with a radical generator such as peroxide, and many of these are sold in Japan. In addition, many findings have been published regarding the use of these materials to impart adhesion to other resins and metal inorganic powders, and a large number of related patent applications have been filed. Examples include Japanese Patent Publication No. 62-5788 and Japanese Patent Publication No. 62-9135.

Also, Japanese Patent Application Laid-open No. 62-101510151 62-1
As seen in Japanese Patent No. 1745, there is also an example in which maleic anhydride is added to a copolymer of ethylene and α-olefin using peroxide or the like to improve the heat resistance and mechanical strength of the composition. These methods simply add a polar group of maleic anhydride to a non-polar resin to increase its affinity with the filler and ultimately improve its mechanical strength and heat resistance. Focusing on hydrated metal compounds, water-mediated bonding,
That is, the present invention is not intended for siloxane bonding of silane graftomers and bonding by complex salt formation based on the reaction of dicarboxylic anhydride derivatives.

[Problem to be solved by the invention]

In order to solve the above-mentioned problems, the present inventors have already developed a flame-retardant composition consisting of an olefin resin, a silane graft tomer of the olefin resin grafted with silane in advance, a hydrated metal compound, and a dicarboxylic acid derivative or dicarboxylic acid anhydride derivative. We have developed olefin resin compositions (patent application 1986).
-45200), the present invention is directed to the surface deterioration and significant chemical resistance of these resin compositions that occur during various environmental tests or during actual use due to the inclusion of a hydrated metal compound useful as a flame retardant. The purpose of the present invention is to provide a flame-retardant resin composition that prevents deterioration of the surface and further improves surface scratches, surface whitening and buckling during bending.

[Means to solve the problem]

The flame-retardant resin composition of the present invention is a composition consisting of the following components [al to (Ql), (a) + (bl 1
00 parts by weight, (0.1 to 30 parts by weight of C1, (d
) and 50 to 300 parts by weight of iQl.

Copolymer of fal ethylene and α-olefin, EEA
or one or more resins selected from ethylene-methyl methacrylate copolymer resins (hereinafter referred to as EMMA) + silane grafted olefin resin silane graftomer TC + polyethylene, IEVA or ethylene-α- 1) Silicone modification ((・) produced by graft polymerizing a reactive polyorganosiloxane to an olefin copolymer maleic acid ffl i form or maleic anhydride derivative fdi thermoplastic resin
Hydrated metal compounds.

In the present invention, the olefin resins used after silane grafting include low-density polyethylene, medium-density polyethylene, high-density polyethylene, copolymers of ethylene and α-olefin, IEVA, F, l':Δ, EM
Examples include M8, ethylene propylene rubber, and ny-ethylene propylene diene rubber.

The α-olefin of the copolymer of ethylene and α-olefin used in the +a+ component, (1)) component, and (e) component includes C3 to C12, such as polypropylene, butene-1, pentene-11, and hexene-1. , heptene-1
, to octene-1,4methylpenteno-1,4methyl-
Examples include 1-cene-1,4-4-dimethylpentene-1, nonene-1, decene-1, ran]-゛cene-1 and l'decene-1. Particularly preferable ones include butene-1, pentene-1, hexene-1, heptene-1
, 4-methylpentene-1.

The silane graftomer used in the present invention is an olefin resin described in "2" with the general formula RR' S r Y2 (R is a monovalent olefin unsaturated hydrocarbon group, Y is a hydrolyzable organic group, and R' is It is obtained by reacting an organic silane represented by a monovalent hydrocarbon other than an aliphatic unsaturated hydrocarbon (or the same thing as Y) in the presence of a free radical-generating compound. This is Special Publication No. 51-24313 fl
i and Japanese Patent Publication No. 48-1711, Japanese Patent Application Publication No. 50-2
This method uses the known method disclosed in Japanese Patent No. 1342, etc., and specifically, for example, using a polyolefin resin as a base and vinyl 1-rimetho-1-sonoran etc. I) CI)
(ii) can be achieved by using in combination a -ff peroxide having a strong polymerization initiating effect such as (Ncumylpero, 1-site).

FUi of Shingraph I-mer is 100 weight liters of resin.
In the ri part, 21Q A% or more is preferable, and if it is less than this, the effect on shape retention properties at high temperatures, j, 'tkchi' and 11g lower resistance 1 is small.

In addition, the rack of Noran Graftomer was also made 3 times C1, 11
7T on the scale of gel content ≦- as residual content
For example, gel content -B 20 jlj lucid tH, ~80 weight 9 stones is preferred.

If the gel fraction is less than 20% by weight, the effect of maintaining shape at high temperatures and preventing sagging during combustion will be weak, and if the gel fraction is more than 80% by weight, moldability will be poor.

If the amount of maleic acid derivative or maleic anhydride derivative added to polyethylene, EVA or ethylene-α-olefin copolymer is less than 0.1 part by weight, the effect will be weak.
If the amount exceeds 1 part by weight, the bonding due to the reaction with the hydrated metal compound will be excessive, resulting in poor extrusion processability and poor appearance during extrusion processing.

In the present invention, the thermoplastic resin to which the reactive polyorganosiloxane is graft-polymerized includes polyethylene, polypropylene, a copolymer of ethylene and α-olefin, and polyolefins such as E V A , E E A , E ki ki 8, etc. Examples include polystyrene, acryl nitrile-butadiene-styrene copolymer resin, and the like. If the amount of modified silicone is less than 0.1 part by weight, the effect will be weak, and if it exceeds 30 parts by weight, it will not show any significant effect exceeding the improvement effect shown by the present invention, and the product will be expensive, so it is not practical. Not.

The hydrated metal compound used in the present invention has a decomposition initiation temperature in the range of 150 to 450°C, and is generally 2M,O,.XH,0 (where M is a metal , m, and n are integers of 1 or more determined by the valence of the metal, and X is a number indicating the contained bound water), or a double salt containing the compound, and specifically, for example, aluminum hydroxide (A7! toy ・31(,0; or Aj
! (OH)z) Magnesium hydroxide (MgO・++, 0
; or Mg(OH), calcium hydroxide (CaO・H
zO or Ca(OH)z), barium hydroxide (
BaO・+(,0 or B a 0 ・9 Hz O)
, zirconium oxide hydrate (ZrO・n Hz O)
, tin oxide hydrate (SnO・I'+20), basic magnesium carbonate (3MffCoffi・Mg (OH
) t ・3H, O), hydrotalcite (6M
gO-Alz Ox ・+120), doutsnight
(N a COI ・A e20i・n I(z O
), borax (N at O・Bz ○,・511.0)
, zinc borate (Zn1140.-22nO), and the like.

If the amount added is less than 50 parts by weight, the desired flame retardant effect cannot be obtained, and if it is more than 300 parts by weight, mechanical properties such as tensile strength will deteriorate, and extrusion processability will deteriorate.

As other additives, the flame retardant composition of the present invention may optionally contain commonly used additives such as antioxidants, neutralizers,
Ultraviolet absorbers, antistatic agents, pigments, dispersants, lubricants, thickeners, foaming agents, metal deterioration inhibitors, fungicides, fluidity regulators, etc., as well as phosphorus and phosphine derivative flame retardants, and other inorganic fillers. , a crosslinking agent, a crosslinking aid, etc., or other synthetic resins may also be included. It is also possible to carry out crosslinking by electron beam irradiation.

The production method includes copolymer of fal ethylene and α-olefin, EEA
or one or more resins selected from EMMA.

(bl Silang grafted olefin resin silane grafted tomer in advance.

tc+cl Maleic acid derivative or maleic anhydride derivative of ethylene, EVA or ethylene-α-olefin copolymer.

A silicone modified product obtained by graft polymerizing a reactive polyorganosiloxane to a tdi thermoplastic resin.

(e) Hydrated metal compound.

Of (+') fal, [bl, (c), (d), (e)
(ii) (during production of silane graftomer of bl) (c)
A method of producing a pellet-shaped silane graftomer by adding one or more of l, (dl) and then kneading it with the remaining components (...) (a), (bl, (e), Any of the manufacturing methods may be used, including a method in which any of the components (d) and (c) is selected and kneaded in advance, and then kneaded with the remaining components.

In addition, compared to conventional technology, the combustion suppression effect is completely different from the combustion suppression effect of carbon powder, and the combustion suppression effect is achieved regardless of the addition of various pigments to make it easy to identify depending on the purpose. Coloring can be freely done according to the needs.

〔Example〕

This will be explained below by giving examples.

EXAMPLE First, a polyolefin resin was prepared according to the formulation shown in Table 1 according to the following procedure. Digyl peroxide (DCP) was dissolved in vinylmethoxysilane, and two types of low-crystalline polyethylene (1) (2) and low-density polyethylene (3) were mixed and stirred as shown in Table 1. Extrusion temperature 150 using a 5 Q amφ extruder
Extruded at ~200°C, pelletized silane graftomer resin A, 3. I got a C. Resins Δ, B, and c were each hermetically sealed in an aluminum laminate bag, stored in a state where external moisture was blocked, and dispensed as needed for use.

+11 Made by Nippon Petrochemical ■Softlex (ethylene-
α~Olefin copolymer) (2) Rexron (EEA) manufactured by Nippon Petrochemical ■ (3) Low density polyethylene manufactured by Sumitomo Chemical Co., Ltd. *As shown in Table 2 by the insoluble residue method after immersion in xylene at 120°C for 20 hours. The various ingredients were mixed all at once in a container, kneaded with a panbari roll, and granulated. The obtained composition was again roll-pressed to prepare various test pieces for measurement.

Using this test piece, we evaluated the degree of surface whitening due to the formation of magnesium carbonate, the change in position when soaked in 10% sulfuric acid and 3% caustic soda aqueous solution, the scratch resistance of the surface, the whitening property on bending, and the flame retardant properties based on the oxygen index. I did it. Further, a tube having an outer diameter of 201 mm, an inner diameter of 18 mm, and a thickness of las was extruded using an extruder, and the extrusion workability and buckling using this extruded tube were evaluated.

As a result, as seen in the examples shown in Table 2, the composition of the present invention showed significant improvements in the degree of whitening, chemical resistance to sulfuric acid and caustic soda, surface scratches, surface whitening during bending, and buckling. I understand that.

(4) Manufactured by Sumima Kagaku Kogyo ■, EMMA (5) Manufactured by Sumiya Kagaku Kogyo ■, low density polyethylene (6) Manufactured by Mitsui Petrochemical Industries (1), maleic anhydride grafted polyolefin VFRl, 3, density 0.94 ethylene-α -Olefin copolymer base (7) Manufactured by Nippon Petrochemical ■, maleic anhydride grafted polyolefin MFR
o, 3, density 0.92, ethylene-α-olefin copolymer base (8) manufactured by Dow Corning ■, silicone modified product based on low-density polyethylene, silicone-containing”ft 40Wt
9% (9) Manufactured by Showa Denko ■, product name: Heijirai) +142
M001 Kyowa Chemical Co., Ltd. 0 Kiku, product name Kiss 75B00 Sanyo Chemical Co., Ltd. Sunwax 17IP 1.0 Ciba Geigy @ Irganox 1076 0.3 Sumitomo Chemical Co., Ltd. Sumilizer WXRO, 30 Pigment For black: VALCAN 9A -323,00j
A press sheet with a thickness of 5 cs
The sample was taken out 48 hours after the injection, and the degree of whitening (formation of magnesium carbonate crystals) was visually observed.

Weight change measurement by 0010wt% sulfuric acid immersion 50℃ x 7
Daily test shape JIS No. 3 dumbbell used l■ Thickness 0513
Weight change measurement due to wt% caustic soda immersion
50°cx7 days test piece shape JI
S No. 3 dumbbell used 1 Ryu Thickness 00 Pencil HB hardness, visual judgment by scratching 0712 am 1g sea) 180
Frequency bending whitening visual test 081 JIS K 7201
by.

Electric wire (conductor diameter 1m-φ solid copper wire with soft vinyl chloride hardness (JIS A) 80 A test sample in which a composition was coated to a thickness of 3 am was prepared, and when this was bent along a mandrel with an outer diameter of 100+nφ, the extent of wrinkles was visually determined.

(2G150ssφ single screw extruder 150-160-1
70-180℃L/D 25 Compression ratio 3.5 Tube extrusion outer diameter 20mmφ, inner diameter 13m5φ Evaluation Excellent>
The order was ``Good'', ``Acceptable'', and ``Fail'', and those up to the level of ``Acceptable'' were considered to have passed.

〔Effect of the invention〕

When the composition of the present invention is molded, (1) the silane graftomer does not require any help from a catalyst to promote crosslinking, and the hydroxyl group (OH group) on the surface of the hydrated metal compound and the ranol group of the silane graftomer ()
Si-OH) due to the influence of the slight moisture on the surface of the hydrated metal compound and the hydrated metal compound similar to the catalyst of the organometallic compound,
In the environment of frictional heat generated during γd kneading, a condensation reaction occurs due to hydrolysis, forming a strong siloxane bond (-5i-0-Mm
On; M metal) is formed. At this time, no catalyst or the like is required at all.

The maleic acid derivative or maleic anhydride of polyethylene, IEVA, or ethylene-α-olefin copolymer, which is a component of +21 tc+, reacts with the metal ion of the hydrated metal compound to form a complex salt.

(3) The modified silicone contributes to improving the wear resistance and moldability of the composition.

As described above, the synergistic effect of the siloxane bond between the silane graftomer and the hydrated metal compound (the bond formed by the complex salt formation between the maleic acid derivative or maleic anhydride derivative, which is a component of C1, and the hydrated metal compound) and the silicone modification This material greatly improves surface deterioration, decrease in chemical resistance, surface scratches, surface whitening and buckling during bending of the flame retardant resin composition.

Patent applicant: Sumitomo Bakelite Co., Ltd. Jaw No. 81190 2, Name of the invention f!Tozosui/olefin resin composition 3, 7 Sanno f: Relationship with the Suru case Patent applicant address 4, 11-36, Mita 3-chome, Minato-ku, Tokyo; Detailed explanation of the invention column 5 of the specification subject to amendment, contents of amendment (1) Meiki'II Kichi No. 3: bottom of page 3, line 63 l1PH2J
a rP If 2J: Correct this.

(2) Specification No. 1 = 'Dicumyl peroxide' in page 1, 61f, is corrected to 'dicumyl peroxide'.

that's all

Claims (1)

[Claims] A composition comprising the following components (a) to (e),
(c) from 0.1 to 100 parts by weight of (a) + (b)
30 parts by weight, 0.1 to 30 parts by weight of (d), and (e)
A flame-retardant olefin resin composition characterized by containing 50 to 300 parts by weight of. (a) One or more resins selected from a copolymer of ethylene and α-olefin, an ethylene-ethyl acrylate copolymer resin, or an ethylene-methyl methacrylate copolymer resin (b) Silane grafted in advance Silang graft tomer of olefin resin (c) Maleic acid derivative or maleic anhydride derivative of polyethylene, ethylene-vinyl acetate copolymer resin or ethylene-α-olefin copolymer (d) Reactive polyorganosiloxane to thermoplastic resin Silicone modified product obtained by graft polymerization (e) Hydrated metal compound